Ten-Step Asymmetric Total Synthesis of (+)-Pepluanol A

The first asymmetric synthesis of pepluanol A (1) is presented. The synthesis route is very concise (10 steps) and features a Curtin-Hammett-driven stereoconvergent intramolecular Diels-Alder reaction. A Nozaki-Hiyama-Kishi reaction comprises the connective step, bringing together the seven-membered enone system bearing the dienophile and the diene in the side chain. Subsequent stereoconvergent IMDA reaction furnishes the carboskeleton of the natural product in only 7 steps. The reactions were carried out on a gram scale up to an advanced intermediate and including the stereoconvergent intramolecular Diels-Alder reaction.